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In an effort to create a non-Fett-family Mandalorian I am seeking advice on paint... but I am NOT seeking advice on a paint scheme - but rather - how to create a paint effect.

That is --- one particular detailed area of my paint scheme in my mind's eye has a near mirror finish black... like Vader's helmet after it's been waxed and buffed a few hundred times shiney black.

So the question is:
How do I create THAT shiney/mirror-like of a finish with black as the primary color??? Is this some sort of layering technique? Super dense layering of clear coats? A mix of silver and black and clear coat?

I used to do autobody and paint for custom cars and Hot Rods a while back. We used to do what was called "2 stage" painting. Basically on a vehicle after the skin was prepped for painting...we started out with either a gold or gray/silver as a base coat. Next we applied the chosen main color mixed with a clear. We would layer that mixture of clear and the chosen color many times very lightly until it we achieved the desired "darkness" or "lightness". It's very important to allow drying time between coats. After we were satified with the color...we next applied several coats of clear. What we achieved was an extremly shiny custom paint job with the illusion of "depth" to it. Almost like a "candy apple" paint job but without the harmful lead of yesteryears technique. Hopefully this technique can help with your costume and if someone has anything to add or update...please jump in as I haven't painted cars since 1992. Good luck!

I do Custom paint on Harleys and other Motorcycles.
you could also use lacquer paints.
With Lacquers, you prep the helmet, use a primer meant for lacquer and spray on your paint. Wet sanding between coats with 1200 grit sandpaper. the more coats of Lacquer, the deeper the finish will appear. Then you move on to the Clear coat, again wet sanding between coats. After this is all cured, a final wet sanding and then a buffing and it will look "WET" and DEEP!
Although I must say, alot of the Urethane Enamel Auto paints now a days give you almost the same look without all the Wet sanding. They are REAL easy to use.
You can buy them in Single stage, basically paint and clear coat mixed, or 2 stage paint and a separate clear.
Keep in mind some paints require a hardener added.
Your best bet might be going to a local Auto paint supplier and asking them what they recommend.
While alot of paints can be loaded into rattle cans, spraying with a quality sprayer will give you the best results. And may I also recommend that what ever brand of paint you buy, buy the Clear coat and primer of the same brand. That way you know there wont be any problems with compatibility.
Hope this helps.
Thanks,
Robert E.